Process of producing chlorinated acetaldehydes utilizing chlorinated acetaldehydes as diluents



Och 21, 1952 J. A. PIANFETTI ETAL PROCESS OF PRODUCING CHLORINATED CETLDEHYDES UTILIZING CHLORINATED ACETALDEHYDES AS DILUENTS Filed oct. 2o, 1948 Mum.

QLNI.

Mmm qu SW Patented Oct. 21, 1.952

UNITED STATES' PATENT OFFICE PROCESS VE ,PRODUCINGV A CHLORINATED ACETA-LJDEHYDES UTILI-ZING CHLORIN- ATED ACETLDEHY DE S` AS v DILUENTS John- A. Pianfettand David JL'Porter,v South Charleston, W; Va;, assignorsto'Food Machinery andi Chemical Corporation; rNew York,- N; Y.,,a:l corporation of Delaware Application'focmberzo, 194s, serial No'. 55,4521

(c1. 26o-toi) 4 Claims; 1.

This invention# relates to the productionl of chlorinated* acetaldehyd'es and; moreI particularly;` totlie pro-duction of chloralfrom-acetaldehyde" and its-reversible polymers.

Tlie`-demand for chloraL- which is'usedasa-n interniediateV in` the `production of r DDT', namely, 2*,'2y -Mbis- (4 chlorophenyl) -1',1,1 trichlo-roethane;` has increasedmaterially' in Erecentyears. Most ofthefchloral'used `for this `and otherfpureven thoughl a'-yielfr'l"not exceeding 'about 35 jper cent based ulixoirtl'i'eL amount ofV alcohol Aused is obtained. Y f

It' is also known from the prior art that chloral'isonem of the' products obtainedY from acetaldehyd-e* when' it is subjected'` to chlorination.` However,4 acetaldehydehas not been used in the commercial productionlof' chloral." The fail-ureto useacetaldehyde for its reversible polymersas araw material for' the production of chloral probably" is 'due-tothe fact that 'yields by knownchlorination 'techniques havefnot been so satisfactoryasthose obtainedlby the ehorinationf of alcohol? In general, thev` prior'V yield' of chloralifrom yacetaldehyde 'wasr tool low` 4to vbeV coninierciall'rY interesting. Apartfrom'- the un'- reacted 'aldehyde,- numerous by-products' which could not be-con'vertedi into chloralf such as'the acetyl chlorideand acetic acid', or condensation products, such asy butyl chloral, were'V produced' in' substantial quantities. The presence of these undesired by=productsfnoton1y reduced thel yield ofthel desired product but 'also introduced-problems ofi separation.

It ris-2a majorobject of? this invention topr'ovi-del'a' lhi'g'hlyV fefticient process for the llarge "scale productiom` of" chlorarl". and otherchlorinated acetaldehydes from `acetaldehyde and its rever-Vv sible polymers.`

It is-another object 0f thisinvention` to provide a process for producingchloral from acetaldehyde and its reversiblepolymers permitting the utilization ofv readily-available, relatively inexpensive apparatus. y

It! is Vafu'rtloer object'of this invention to provide"a'piocssfor'producing Chloral from acetaldehyde andr 'its' reversible polymers at elevated teinfipera'tures"makingv the process" highly` eili'cient without involving explosion hazards.

Yet another object of this invention" is to'produce chloral frcmjacetaldehydeand its reversible polymers underA conditions which preclude or inhibit polymerization of chloral.

It is t'a Lspecialfobject of this invention: to`r producefhigh yields of `chloral vin' a 'relativelyshort 2. period -fof time, while minimizing: the production ofV undesirable by-products.

Other objects and features of the invention will be obvious from thermore` detailed description which follows.

Wel have discovered that fchloral can be pro'- duced' -froma'cetaldeh'ydeand its' reversible polymerslwhi'ch depolyrn'erize under chlorination in commercially* interesting' yields in a` relatively short 'period of time by chlorinating the aldehyde with sufli'ci'ent chlorine to 4 convert the available ald'eh'yde."into`v chloral without the necessity of conftrolling'the` initial 'chlorination' temperatures and adyantageously at initial chlorinatingI temperatures-vof 50 C. or'mOre. A major proportion of the-acetaldehyde-"or itsf reversible polymersiis readily converted ir'itovclolora'l,v and yields equalingior" exceeding'.v 75'1per cent are normally obtained. These results` are f obtained" by.v using a chloroacetaldehyde such as chloral' as a diluent. The amountof-diluent usedv varies with the apparatusand with. thelchlor'ination temperature; but vcustomarily at least3-54 to Limols of the chlorcacetal'd'ehyde should be present for' every mol- 'equivalent of acetaldeh'yde introduced.'

In-YA the commercial operation of the process, chlorine and acetaldehydearer a'dded continu*- ously-fto a previously 1 chlorinated acetaldehyde, an'd, asfa Iresult;V the amount l of. Adiluent present is far irl-excess ot theminiinum amount neces-A sary.

Theoretically, ati least .3 mol's of* chlorine per mol equivalen'tof v'acetaldelfiyde is'required' in the instant process' to convert thelacetal'dehydey or its" reversible polymers tochloral.` However; due tofthe i vfact- 1 part Lofritne facetaldehyde orf its reversible ipolymers'is i converted into undesirable byl'produ'cts:utilizing-lessthaol 3 m'ols of chlorine andfcer-tain amounts Aofaldehyd'e arelos't in the ch1orifnation-, it is f difcuitto specify a vparticula'r'amount' of chlorine to produce` ah satisfactory?" yield?` of a desired# chlorinated product. Normally the-efficient operation of the prooess requires' lthatoa' slight excess of 'chlorine 'be lus'ed, since it? is" diicult to? regulate the ratev ofV flow of" 1 the chlorine f gas such? that all ofi 4it is "consunied`A` inr` the reaction and yetlno unreaoted aldehyde 'existsj i o o B'y-using the chlorination productief acetaldehyde or itsv reversible' polymers,Y sometimes referredto` herein as a chloroacetaldeliyde,` problems of refining the 'crudeproduct and separating undesired products'are signiiicantly reduced. When u'singa chlorinated aldehydeas thediluent and introducing the "chlorineand aldelyde in a ratio sufficient to convert the aldehyde to chloroacetaldehyde, the concentration of the aldehyde present in the reaction mass is always maintained as low as found necessary or desirable, and conditions found conducive to the formation of the desired chlorination products are maintained and the formation of undesired by-products inhibited. When using anhydrous conditions and chlorinated acetaldehydes as diluents, ordinary metals, such as nickel, Monel metal, and the like, may be used in the reaction apparatus. In the presence of water, substantially more expensive apparatus is necessary, such as chlorinators made of a furane resin filled with asbestos and known as I-Iaveg 60.

The reaction may be initiated at room temperatures and the temperatures permitted to rise as a result of the exothermic heat of chlorination. Where it is desired to lessen the chlorination cycle and prevent polymerization of chloral, however, chlorination is initiated at temperatures of at' least 502C. or even at 80 C. and more.

In order to obtain high yields of chloral, it is necessary to use reaction-promoting substances or other reaction-promoting techniques at least in the later stage of the process. A preferred class of reaction-promoting substances is metal chlorides, such as those of iron, zinc, antimony, tin, and chlorides of phosphorus or mixtures thereof. Antimony trichloride has proved to be especially advantageous. Generally speaking, not more than per cent of the metal chlorides as compared to the weight of acetaldehyde can be used economically in the process. By using such reaction-promoters, yields of the order previously mentioned can be obtained without operating at temperatures in excess of the boiling point of the diluents used or that of the reaction mass.

Water offers a cheap reaction-promoting substance but is not preferred, since its presence apparently favors the formation of undesirable byproducts and necessitates a more involved procedure for the purification of the chloral than would otherwise be necessary. When Water is used as a reaction-promoter, it is customarily used in molar proportions not exceeding l to 3 mols per mol of acetaldehyde or its equivalent, although larger proportions may be used.

Among the other reaction-promoting techniques is chlorination at temperatures above the normal boiling point of the reaction mass.

The present process is advantageously operated by having chlorine, acetaldehyde, or its reversible polymers, and a reaction-promoting agent introduced continuously into the system and the reaction product continuously withdrawn therefrom. In such a continuous system a single reactor may be used, but it is preferable to use at least two reactors with part of the chlorine necessary to convertI the aldehyde to chloral being introduced into each of the reactors. The reaction-promoting agent may be introduced into either or both of the reactors. More than two reactors may be used but generally are not necessary. When using the plurality of reactors to produce chloral, substantially all of the diohloroacetaldehyde, which is difficult to separate from the chloral, may be converted to chloral, the amount remaining being reduced to l per cent or less of the original aldehyde.

The process can be operated with an intermittent, rather than continuous, addition of the aldehyde. The preferred procedure for this mode of operation involves adding the a1- dehyde to a relatively large volume of the chlorination product, chlorinating until the desired chlorination product is reached, withdrawing enough material to reduce the content of the reactor to the same volume as that present before the addition of aldehyde, and then repeating the cycle. This intermittent technique is a type of continuous operation.

The reaction-promoter may be added in the same manner.

Ii the instant process is carried out continuously, there is not much danger of explosions except possibly when starting up the chlorination, since, after a steady state is reached, hydrogen chloride is evolved continuously and dilutes the chlorine-aldehyde vapors to such an extent that they are not explosive. In a special embodiment involving continuous chlorination at about to C. in a body of liquid consisting principally of chloral, there is no danger of explosions, even when initiating the process, since the vapor pressure of chloral is so high as to preclude the possibility of an explosive mixture of chlorine and aldehyde vapors. Likewise, where the diluent is the chlorination product of acetaldehyde or its reversible polymer, especially chlorination products containing a substantial amount of chloral, explosive mixtures are not formed. The absence of explosive conditions when operating in accordance With preferred procedures described herein constitutes a special feature of this invention.

In the operation of our process, paraldehyde is preferably used, although kindred yields can be obtained from acetaldehyde. Acetaldehyde is more difficult to handle, and the reaction is more diflcult to control.

In a typical operation two connected reactors provided with agitators, vent valves, and so forth are used. The desired amount of chlorinated acetaldehyde, such as monochloroacetaldehyde, dichloroacetaldehyde, or preferably chloral, to be used as a diluent is introduced into the iirst reactor. The aldehyde and about 2.3 per cent of the weight thereof of antimony trichloride are introduced continuously or semicontinuously, l. e., intermittently, into the rst reactor. The desired amount of chlorine is continuously introduced into the two reactors, the larger portion being introduced into the rst reactor. The chlorine is introduced into the second reactor only after it has become about one-fourth filled as an overflow from the first reactor. Hydrogen chloride is evolved from each of the reactors. The rate of flow or" the chlorinated material from the rst reactor to the second reactor is determined by the rate of introduction of the various ingredients. The average retention time of the liquid in each chlorinator is adjusted to approximately ninety-six hours, and each reactor is maintained at a temperature of approximately 80 to 85 C. The crude chloral leaving the second chlorinator is puried by vacuum rectification. By proceeding in this manner, chloral approximating 75 per cent and higher of the theoretical yield is obtained, While less than l per cent of the original aldehyde remains as diohloroacetaldehyde,

We have discovered that when high yields of chloral are` desired in a continuous process with most advantageous use of the apparatus, it is necessary to introduce part of the chlorine after substantially all of the acetaldehyde material has '22 toa condenser 23.

heen' converted into a chlroacetaldhyd; In our process we 'complete the chlorinationin a second chlorinator, but it is apparent that -such a procedure is Aa special embodiment of" a system for introducing part of the chlorine at intermediate points along the'path of flowv in the sys'- txn For example, it is estimated it will take four times as long'to obtain the ysame degree of chlorinationa single-reactor or chlorinator as ittakes with two reactors in ser-ies; or, saying lit differently, twoV chlorinators series will produce twice as Hmuchof a desired' chlorinated product as two reactors of the saine size in parallel'.

The invention will be readily understood -from a description of the practical operation of the process as applied to a preferred procedure. In thedescription reference will be made to the acycompanyingdrawing wherein the apparatus 'and connections are diagrammati-call'y illustrated.

Paralclehyde is continuouslyfedf into the first chlorinator l0.' through. conduit H. Simultane- Iouslyv chlorine isl led froml aV source Vof'supply (not shown) rthrough line' l2 and thence partially rthrough line l'3 into the flistchlornator P0 and partially 'through line I4. linto the second chlorinator i; The chlorinators and the connecting conduits in the systemido not lhave to he highly chemically resistant and may be made of metal such as nickel or. Monel metal. Antimony chloride 4is continuously or intermittently introduced into the'iirst chlorinator IIJ through conduit i6. Partially chlorinated aldehyde and antimony ychloride are withdrawn from the rst chlorinator I0 through conduitA Il' and. introduced into the second. chlorinator i5.

r'Ihe material'in the frst' chlorinator lo and in rthe Asecond chlorinator 'I5 is agitated and mixed lby a circulating system generally designated by i8 and I9, respectively. If necessary, the iiuid flowing through the circulating system may be lprovided with heating or cooling means to con*- trol the temperature of the: reaction mass.Y

v The` gaseous hydrogenchlorideformed in the 'chlorination of the paraldehyde together with certain amountsl of the unchlorinatcd aldehyde and partially chlorinated aldehyde is withdrawn from the first chlorinatorA l0 through conduit '2Q and. from the second chlorinator i5 through con'- -duit 2l and is thence conveyed through conduit The gaseous hydrogen chloride. and unused chlorine pass through the condenser and are withdrawn through conduit {'24. These gaseousmaterials may be collected or lpassed intoV the atmosphere. The 'condensed aldehyde and partially chlorinated aldehyde flow back into the Vfirst chlorinator lo through con- `duit 2`5. v

The chlorinated material is withdrawn from the second chlorinator l5 through conduit 25 land introduced into-storage tank 21.-

`When it is desiredV to purify the chlorinated material, it is withdrawn from tank 21 through conduit 28 and introduced intof a vacuum. distillation tower 29. Distillation customarily takes lplace lat temperatures ofthe orderof 1,00*o C. and under a pressure of approximately 100 to 120 millimeters of mercury. The lower boiling fractions from the. distillation tower 29 .pass through conduit 3U toa condensing system 3i, where the vapors are liquefied. The liquids now through conduit 32, where part, constituting the chlorinated product; is withdrawn through conduit" 33 andthe remainder reintroduced into tower l2!! through conduit 3'4. The impurities,

suchashutyl chloral and other highboiling fractions.. flow from the bottom of tower 29I through 6 conduit 35 into heater IStan-d may be withdrawn rtherefrornthrough conduit 371.v 1

In. such a system yields of chloi'al. of.Y high lpurity equaling orexceeding Ito. 80y per.` cen-t Ibased on the quantity of aldehydeused caribe lproduced with an average retention time in each lchlorinator of three and a. third to four days(- The following examples further illustratethe operation of the process.

Example' 1 Into an operating cli-Iorinati'n'g system for 'the production of chloral, such as that illustrated'in the diagrammatic representation, chlorineV and paraldeh'yde are fed in a mol ratio of about 9 to rl. The chlorine is divided such 'that' from 'about v5 to l0 per cent is introduced intothe second chlorinator. The mixtures in the chlorinator. are lmaintained aty a temperature of about v825C. Antimony tr-ichl'orid'e at the rate of abouty 2.5 parts per 100 vparts of paraldehyde is'add'ed 'to the 'rst chlorinator. The` partially chlorinated mii'rture from the rfst chlorinator and inter- `mixed antimony trichl'oride are withdrawn into the second chlorinator so as tof maintain the volume Vin the first chlorinator substantially constant. The feed rates are such that the average time of retention of the material' in the chlorinators is of the order of three to four` ldays. `The dichloro'acetaldehyde can be reduced 'to a very low percentage, say, of the order of l' to' 2 per cent of the chloraL dependent upon the average time vof retention in the chlorinators.

By operating in accordance with this system, the amount of butyl chloral andl other high boiling fractions can also be reduced to a very low percentage, say, of the order of several per cent. The yield of chloral from the system is of the lorder of '70 to 80 per cent or more based upon the amount of aldehyde used. Thev conversion of the aldehyde to the chlorinated aldehyde is substantially complete. The yield of chloral is less than that theoretically possible primarily due to the fact. that a certain amount of the Valdehyde and chlorinated aldehydes escapes with the gaseous `oy-products. Additionally, it is dilcult to 'completely separate the chloral from the high boiling Iby-products. Thus it can be said that theyield is substantially quantitative when considered apart from the inefficiencies inherent in lthe apparatus.

Example' 2 Chlorine and paraldehyde are vfed in a `molratio of about 9 to 1 into a chlorination vessel initially filled with chloroacetaldehydes consisting primarily of chloral and maintained at a temperature of C. Antimonyv trichloride at the rate of 2.3 grams per grams ofparaldehyde is 'also added. The product is withdrawn continuously to maintain a constant volume in the reactor. The feed rates are such that the average time of retention ofthe material in the chlorinator is 273 hours. 'The chloral and dichloroacetaldehyde in the product under certain circumstances represent 59 per cent and 4 per cent, respectively, of the original aldehyde. When such yields are obtained, only 2 per cent' of the 'p-araldehyde is converted to butyl chloral and approximately 3 per cent to acetic acid.

,per centof` chloral and 1l per cent of' dichloroacetal'dehyde 1 Example 3 pon repeating the chlorination described in Example 2 with a retention time oi sixty-eight hours, the chloral and dichloroacetaldehyde in the reaction product typically represent 70 per cent and 6 per cent, respectively, of the original paraldehyde, although yields as low as 59 per cent and 15 per cent, respectively, are at times obtained.

Eample 4 The operations described in Example 2 were repeated with a second chlorinator in series with the rst. The chlorine feed was divided between the two, the greater part going to the rst chlorinator. Customarily from 5 to l0 per cent of chlorine is introduced into the second reactor. The retention time in each chlorinator was sixtyeight hours. The chloral and dichloroacetaldehyde in the product represent 78 per cent and 0.6 per cent, respectively, of the original paraldehyde.

In the illustrative embodiments of the examples where the aldehyde is converted into chloroacetaldehyde in one reactor and the chlorinated acetaldehyde more highly chlorinated in a succeeding reactor, the iirst stage of the chlorination could be eliminated by procuring chloroacetaldehydes from other sources, such as mcnochloroacetaldehyde produced from vinyl chloride and hypochlorous acid. When the second stage above is used, diluents are unnecessary, since the chloroacetaldehydes apparently undergo undesired side reactions, such as oxidation to acetic acid or condensation reactions, much less readily than the unchlorinated aldehyde.

The preferred diluent used in our process is the chlorination product of the acetaldehyde or its reversible polymer. In using such diluents, problems of refining the crude product and separating undesired products are significantly re- L duced. When using chlorinated aldehydes as the diluent and introducing the chlorine and aldehyde in a ratio sufficient to convert the aldehyde to chloroacetaldehyde, the concentration of the aldehyde present in the reaction mass is always maintained as low as found necessary or desirable, and conditions found conducive to the formation of the desired chlorination products are maintained and the formation ofundesired by-prodf ucts seemingly inhibited. Other liquid diluents which are miscible with the aldehyde or its chlorination product may be used, however, such as acetic acid, organic solvents such as carbon tetrachloride, inorganic material such as water, and the like. When diluents other than the products of the chlorination are used, it is citen difficult to separate them from the reaction mass, particularly when water is used; and, as a result, anhydrous diluents are preferred, such as certain organic liquids.

It will be understood that acetaldehyde and its reversible polymers encompass monomeric acetaldehyde having the formula CHsCHO and those polymers having the formula (CHaCHCDn which may be made reversibly from it, such as paraldehyde, metaldehyde, and the like. When metaldehyde is used in the process, it is preferably used in a liquid medium. l

This application is a continuation-in-part of our application Serial No. 745,726, led May 3, 1947.

The foregoing description constituting illustrative embodiments of the invention is not to be considered a limitation upon the invention, for the invention contemplates Various adaptations,

8 alterations, and modifications within the scope of the invention which is defined by the appended claims.

We claim:

1. In a process 4for the chlorination oa substance selected from the group consisting of acetaldenyde and its reversible polymers, the steps which comprise continuously adding said substance to a body of at least 3.5 mols of chloroacetaldehyde per mol equivalent of acetaldehyde, continuously adding more than enough chlorine to said body to convert the added substance to monochloroacetaldehyde but less than enough chlorine to convert said substance to chloral, and chlorinating said substance in said body at temperatures of at least 50 C. in the presence of a reaction promoter, continuously withdrawing the chlorinated substance from said body and continuously adding chlorine to the withdrawn substance and further chlorinating the withdrawn substance at temperature in excess of 50 C.

2. In a continuous process for the chlorination of a substance selected from the group consisting of acetaldehyde and its reversible polymers the steps comprising continuously feeding said substance into a reactor which contains a chloroacetaldehyde in a quantity equaling at least 3.5 to 4.0 mols of chloroacetaldehyde per mol of added substance expressed as mol equivalents of acetaldehyde, continuously introducing chlorine into said reactor in a quantity greater than one half the quantity necessary to convert said substance into chloral but less than enough chlorine to convert said substance to chloral and eiectuating chlorination therein at temperatures of at least 50 C., continuously withdrawing some of the product from said reactor including dichloroacetaldehyde, and continuously converting the withdrawn product to chloral in the presence of a reaction promoter by continuously introducing chlorine into the withdrawn product at temperatures in excess of 50 C. until substantially all of the dichloroacetaldehyde is converted to chloral.

3. In a continuous process for the chlorination of a substance selected from the group consisting of acetaldehyde and ,its reversible polymers the steps comprising continuously feeding said substance into a reactor which contains a chloroacetaldehyde in a quantity equaling at least 3.5 to 4.0 mols of chloroacetaldehyde per mol of added substance expressed as mol equivalents of acetaldehyde, continuously introducing chlorine into said reactor in a quantity greater than one half the quantity necessary to convert said substance into chloral and eiectuating chlorination therein at temperatures of at least 50 C., continuously withdrawing some of the product from said reactor, and continuously converting the withdrawn product to chloral at temperatures of at least 50 C. by continuously introducing chlorine into the withdrawn product in the presence of a chlorination catalyst selected from the group consisting of the chlorides of iron, zinc, tin, antimony and phosphorus until the total amount of chlorine introduced substantially equals but does not substantially exceed the amount necessary to convert the added substance to chloral.

4. A continuous multistage process for producing chloral from a substance selected from the group consisting of acetaldehyde and its reversible polymers comprising continuously adding said substance and chlorine to one stage of a reaction system and mixing said substance and chlorine therein with a reaction-promoter selected from the group consisting of the chlorides of iron, Zinc, antimony, tin and phosphorus and an amount of a non-aqueous liquid diluent inert to Said substance and its chlorination products sufficient to substantially prevent deleterious side reactions at the temperatures used, chlorinating said substance in said stage of the reaction system until it is converted to a chlorinated acetaldehyde, continuously withdrawing said chlorinated i substance and reaction-promoter, and introducing them into another stage of the reaction system, introducing chlorine in said other stage, and continuing the chlorination of said chlorinated aldehyde in said other stage until a major portion of said chlorinated aldehyde is converted into chloral, the chlorination taking place substantially throughout said stages at temperatures in excess of 50 C.

JOHN A. PIANFETTI.

DAVID J. PORTER.

REFERENCES CITED The following references are of record in the le of this patent:

19 UNITED STATES APA'I'EN'I'S Number Name Date 2,448,183 Cass June 15, 1948 2,478,741 Brothman Aug. 9, 1949 2,552,934 Cave et al May 15, 1951 FOREIGN PATENTS Number Country Date 576,805 Great Britain Apr. 18, 1946l 581,431 Great Britain Oct. l1, 1946 OTHER REFERENCES Wurtz et al.: Compt. Rend. 74, pp. 777-84 (1872) Pinner: Liebigs Annalen, Vol. 179-180, pp. 24,

Kiss et al.: Chemical Abstracts, vol. 35, p. 2059 Callaham: Chem. and Met. Eng., Oct. 1944, pp.

Schulz: P. B. Report 70309 July 18, 1947, Frame Shchukina: Chem. Abstracts, vol. 43, p. 2575 (Apr. 

1. IN A PROCESS FOR THE CHLORINATION OF SUBSTANCE SELECTED FROM THE GROUP CONSISTING OF ACETALDEHYDE AND ITS REVERSIBLE POLYMERS, THE STEPS WHICH COMPRISE CONTINUOUSLY ADDING SAID SUBSTANCE TO A BODY OF AT LEAST 3.5 MOLS OF CHLOROACETALDEHYDE PER MOL EQUIVALENT OF ACETALDEHYDE, CONTINUOUSLY ADDING MORE THAN ENOUGH CHLORINE TO SAID BODY TO CONVERT THE ADDED SUBSTANCE TO MONOCHLOROACETALDEHYDE BUT LESS THAN ENOUGH CHLORINE TO CONVERT SAID SUBSTANCE TO CHLORAL, AND CHLORINATING SAID SUBSTANCE IN SAID BODY AT TEMPERATURES OF AT LEAST 50* C. IN THE PRESENCE OF A REACTION PROMOTER, CONTINUOUSLY WITHDRAWING THE CHLORINATED SUBSTANCE FROM SAID BODY AND CONTINUOUSLY ADDING CHLORINE TO THE WIDTHDRAWN SUBSTANCE AND FURTHER CHLORINATING THE WITHDRAWN SUBSTANCE AT TEMPERATURE IN EXCESS OF 50* C. 